Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

• the present invention relates to new triazole derivatives, their manufacture, and insecticidal agents containing insecticidal active ingredients selected from the group consisting of carbamates, phosphoric (phosphonic) (di)(thio) acid esters, pyrethrins, pyrethroids, ⁇ -alkylphenyl acetates, ⁇ -cyclopropylphenyl acetates and chlorinated hydrocarbons, and, to increase the insecticidal action of these active ingredients, triazole derivatives.
• insecticidal active ingredients selected from the group consisting of carbamates, phosphoric (phosphonic) (di)(thio) acid esters, pyrethrins, pyrethroids, ⁇ -alkylphenyl acetates, ⁇ -cyclopropylphenyl acetates and chlorinated hydrocarbons, and, to increase the insecticidal action of these active ingredients, triazole derivatives.
• synergism it is known that, when chemical active ingredients are used to combat injurious organisms, mixtures thereof sometimes have a much greater effect than was to be expected from an addition of the individual actions. Such an increase in action is termed synergism. It is not necessary for the synergist itself to have a recognizable action on the organism to be combated.
• Piperonyl dioxide which increases the action of pyrethrins, is of particular importance.
• the triazole derivatives of the formula I and the salts thereof are extremely effective synergists having a wide area of action.
• they increase the action of insecticides from the group consisting of phosphoric or phosphonic acid esters and the corresponding thio or dithio esters, pyrethrins, pyrethroids, ⁇ -alkylphenyl acetates, ⁇ -cyclopropylphenyl acetates and chlorinated hydrocarbons.
• Suitable synergistic triazole derivatives of the formula I are 1,2,4-triazoles, or salts thereof, which bear, in the 1-position, benzyl mono- or polysubstituted on the phenyl ring by linear or branched alkyl of 1 to 4 carbon atoms, preferably in the 4-position, 1-phenylethyl, 2-phenyl-2-chloroethyl, 3-phenylethyl, 2-phenylvinyl, 3-phenyl-2-propenyl, or 2-phenyl-2-propenyl.
• the 2-phenylvinyl, 3-phenyl-2-propenyl and 2-phenyl-2-propenyl radicals may bear one or several halogen substituents, preferably chlorine or fluorine, and especially chlorine, on the phenyl nucleus.
• Suitable salts of triazole derivatives of the formula I are those with inorganic or organic acids.
• examples of such acids are hydrogen halides, especially hydrogen chloride and hydrogen bromide, nitric acid, sulfuric acid, oxalic acid, trichloroacetic acid, and aryl- or alkylsulfonic acids, especially p-toluenesulfonic acid and dodecylsulfonic acid.
• triazoles suitable as synergists are 1-(4-methylbenzyl)-1,2,4-triazole, 1-(4-ethylbenzyl)-1,2,4-triazole, 1-(4-tert-butylbenzyl)-1,2,4-triazole, 1-(3-phenylpropyl)-1,2,4-triazole, 1-(1-phenylethyl)-1,2,4-triazole, 1-(3-phenyl-2-propenyl)-1,2,4-triazole, 1-(2-phenyl-2-propenyl)-1,2,4-triazole, 1-(2-phenyl-2-chloroethyl)-1,2,4-triazole, 1-[2-(2,4-dichlorophenyl)-vinyl]-1,2,4-triazole, and 1-[2-(4-fluorophenyl)-vinyl]-1,2,4-triazole, and salts, especially hydrochlorides, of these compounds
• the reaction is carried out in the presence of an acid-binding agent, for example an organic base, such as triethylamine and N,N-dimethylaniline, or an inorganic base, for example an alkali metal carbonate or bicarbonate, such as sodium carbonate or bicarbonate, or potassium carbonate or bicarbonate, or an alkaline earth metal hydroxide, and in the presence of a solvent or diluent.
• an acid-binding agent for example an organic base, such as triethylamine and N,N-dimethylaniline
• an inorganic base for example an alkali metal carbonate or bicarbonate, such as sodium carbonate or bicarbonate, or potassium carbonate or bicarbonate, or an alkaline earth metal hydroxide
• Suitable solvents or diluents are esters, such as ethyl acetate; alcohols, such as methanol, ethanol, isobutanol and glycol; ketones, such as acetone and cyclohexanone; ethers, such as tetrahydrofuran and dioxane; toluene, acetonitrile, dimethylformamide and water.
• Triazole derivatives of the formula I in which R denotes 2-phenylvinyl which is unsubstituted or substituted by halogen on the phenyl ring are obtained by reaction of compounds of the formula ##STR3## where Y and Z denote halogen, especially chlorine, and n denotes one of the integers, 0, 1 and 2, with a dehydrohalogenating agent, preferably a strong base, in the presence of a solvent or diluent.
• Suitable bases are alkali metal hydroxides, such as sodium and potassium hydroxide, alkali metal and alkaline earth metal alcoholates, such as sodium methylate, magnesium methylate and potassium tert-butylate, or organic bases, such as triethylamine.
• Suitable solvents or diluents are, in addition to water, especially alcohols, such as methanol; ethers, such as tetrahydrofuran and dioxane; methyl glycol and aprotic-dipolar solvents, such as dimethylformamide, acetonitrile, N-methylpyrrolidone and dimethyl sulfoxide.
• alcohols such as methanol
• ethers such as tetrahydrofuran and dioxane
• methyl glycol and aprotic-dipolar solvents such as dimethylformamide, acetonitrile, N-methylpyrrolidone and dimethyl sulfoxide.
• Triazole derivatives of the formula I in which R denotes substituted 2-phenylvinyl may also be obtained by elimination of water or acid from compounds of the formula II in which Y denotes hydroxyl or esterified hydroxyl. Water or acid elimination is advantageously carried out with the aid of a strong acid or a base.
• Suitable acids are for example inorganic acids, such as sulfuric acid, hydrochloric acid and phosphoric acid, and aryl- or alkylsulfonic acids, such as p-toluenesulfonic acid, and suitable bases are alcoholates, such as alkali metal or alkaline earth metal alcoholates.
• a mixture of 14 parts by weight of 1,2,4-triazole, 200 parts by weight of acetonitrile, 32 parts by weight of potassium carbonate and 40 parts by weight of 3-phenylpropyl bromide is stirred for 12 hours. The mixture is then filtered and the filtrate is concentrated. Distillation gives 25 parts by weight of pure 1-(3-phenylpropyl)-1,2,4-triazole; b.p. (0.013 mbar): 114°-116° C.
• insecticidal active ingredients the effectiveness of which can be increased by the triazole derivatives of the formula I are carbamates, such as aryl-N-methylcarbamates, N,N-dimethylcarbamates of hydroxyheterocycles or of enols, oxime carbamates, e.g., 1-naphthyl-N-methylcarbamate, m-tolyl-N-methylcarbamate, 2-isopropylphenyl-N-methylcarbamate, 2-sec.-butylphenyl-N-methylcarbamate, 3-(1-methylbutyl)-phenyl-N-methylcarbamate, o-chlorophenyl-N-methylcarbamate, 3,4-dimethylphenyl-N-methylcarbamate, 3,5-diethylphenyl-N-methylcarbamate, 3-isopropyl-5-methylphenyl-N-methylcarbamate, 6-chloro-3,4-xylyl-N-
• phosphoric or phosphonic acid esters and the corresponding thio or dithio esters e.g. O,O-dimethyl-O-(1-methyl)-2-carbomethoxyvinyl)-phosphate, O,O-dimethyl-S-(N-methylcarbamoylmethyl)-phosphorodithioate, O,O-dimethyl-S-(N-methoxyethylcarbamoylmethyl)-phosphorodithioate, O,O-dimethyl-S-(N-formyl-N-methylcarbamoylmethylphosphorodithioate, O,O-dimethyl-O-[1-methyl-2-(methylcarbamoyl)-vinyl]-phosphate, O,O-dimethyl-O-[(1-methyl-2-dimethylcarbamoyl)-vinyl]-phosphate, O,O-dimethyl-[(1-methyl-2-dimethylcarbamoyl)-
• pyrethrins e.g., an active ingredient mixture consisting of pyrethrin I, pyrethrin II, cinerin I and cinerin II from Chrysanthemum cinerae folium flowers;
• esters of 2,2-dimethyl-3-(2,2-dimethylvinyl)-chloropropanecarboxylic acid e.g., 2-allyl-3-methylcyclopenten-(2)-on-1-yl-(4)-chrysanthemate, 3,4,5,6-tetrahydrophthalimidomethyl-DL-cis,trans-chrysanthemate, 5-benzylfuryl-(3-methyl-DL-cis,trans-chrysanthemate, and 2-methyl-5-(2-propynyl)-3-furylmethyl-chrysanthemate, or esters of 2,2-dimethyl-3-(2,2-dihalovinyl)-cyclopropanecarboxylic acid, e.g., 3-phenoxybenzyl ( ⁇ )-cis,trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylate, ⁇ -cyano-3-phenoxy
• ⁇ -alkylphenyl acetates e.g., ⁇ -isopropylphenyl acetate, especially ⁇ -cyano-3-phenoxybenzyl- ⁇ -isopropyl-4-chlorophenyl acetate, 3-phenoxybenzyl- ⁇ -isopropyl-4-chlorophenyl acetate, 5-benzyl-3-furylmethyl- ⁇ -isopropyl-4-chlorophenyl acetate, 5-benzyl-3-furylmethyl- ⁇ -isopropyl-4-methylphenyl acetate, 3-phenoxybenzyl- ⁇ -isopropyl-4-methylphenyl acetate, 3-phenoxybenzyl- ⁇ -isopropyl-4-methoxyphenyl acetate, and 5-benzyl-3-methylfuryl- ⁇ -isopropyl-4-methoxyphenyl acetate;
• ⁇ -cyclopropylphenyl acetates e.g., ⁇ -cyano-3-phenoxybenzyl- ⁇ -cyclopropyl-4-chlorophenyl acetate, 5-benzyl-3-furylmethyl- ⁇ -cyclopropyl-4-chlorophenyl acetate, and ⁇ -cyano-3-phenoxybenzyl- ⁇ -cyclopropyl-4-bromophenyl acetate;
• chlorinated hydrocarbons e.g., ⁇ -hexachlorocyclohexane, 1,1-di-(p-methoxyphenyl)-2,2,2-trichloroethane, and 6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin-3-oxide.
• Triazole derivatives, or salts thereof, and insecticidal active ingredients may be employed in the agents according to the invention in relatively wide ratios. However, a ratio outside the range of from 1:10 to 10:1 parts by weight will probably seldom be of use. The preferred ratio range is from 1:5 to 5:1 parts by weight.
• the insecticidal agents according to the invention may be used on a variety of plant and household pests. They may be applied as such, in the form of formulations, or of ready-to-use application forms prepared therefrom, e.g., directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used. Triazole derivatives and insecticidal active ingredient, or formulations thereof, may be applied separately or together.
• the formulations generally contain from 0.1 to 95, and preferably 0.5 to 90%, by weight of active ingredient and synergist.
• the amount of synergist and active ingredient in the ready-to-use formulations may vary within a wide range; it is generally from 0.0001 to 10%, preferably from 0.01 to 1%.
• agents according to the invention may also be successfully used in the ultra-low volume method, where it is possible to apply formulations containing more than 95% of synergist and active ingredient, or even a mixture consisting just of synergist and active ingredient.
• mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin
• aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc.
• strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidione, water, etc. are suitable.
• Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water.
• emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers.
• Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
• surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalane derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulf
• Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
• Granules e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers.
• solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
• mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomace
• agents according to the invention may be added to the agents according to the invention (if desired, immediately before use (tankmix) oils of various types, herbicides, fungicides, other insecticides, and bactericides. These agents may be added to the agents according to the invention in a ratio by weight of from 1:10 to 10:1.
• insecticidal agents facilitates the control of plant and household pests.
• these are injurious insects from the Lepidoptera order, e.g., Plutella maculipennis, Leucoptera coffeella, Hyponomeuta malinellus, Argyresthia conjugella, Sitotroga cerealalla, Phthorimea operculella, Capua reticulana, Sparganothis pilleriana, Cacoecia murinana, Tortrix viridana, Clysia ambiguella, Evetria buoliana, Polychrosis botrana, Cydia pomenella, Laspeyresia molesta, Laspeyresia funebrana, Ostrinia nubilalis, Loxostege sticticalis, Ephestia kuehniella, Chilo suppressalis, Galleria mellonella, Malacosoma neustria, De
• examples from the Coleoptera order are Blitophaga undata, Melanotus communis, Limonius californicus, Agriotes lineatus, Agricotes obscurus, Agrilus sinuatus, Meligethes aeneus, Atomaria linearis, Epilachna varivestris, Phyllopertha horticola, Popillia japonica, Melolontha melolontha, Melolontha hippocastani, Amphimallus solstitialis, Crioceris asparagi, Lema melanopus, Leptinotarsa decemlineata, Phaedon cochleariae, Phyllotreta nemorum, Chaetocnema tibbialis, Phylloides chrysocephala, Diabrotica 12-punctata, Cassida nebulosa, Bruchus lentis, Bruchus rufimanus, Bruchu
• Examples from the Diptera order are Myetiola destructor, Dasyneura brassicae, Contarinia tritici, Haplodiplosis equestris, Tripula paludosa, Tipula oleracea, Dacus cucurbitae, Dacus oleae, Ceratitis capitata, Rhagoletis cerasi, Rhagoletis pomonella, Anastrepha ludens, Oscinella frit, Phorbia coarctata, Phorbia antiqua, Phorbia brassicae, and Pegomya hyoscyami;
• Hymenoptera order examples from the Hymenoptera order are Athalia rosae, Haplocampa minuta, Monomorium pharaonis, Solenopsis geminata, and Atta sexdens;
• Nezara viridula examples from the Heteroptera order are Nezara viridula, Eurygaster integriceps, Blissus leucoterus, Dysdercus cingulatus, Piesma quadrata, and Lygus pratensis;
• examples from the Homoptera order are Perkinsiella saccharicida, Nilaparvata lugens, Empoasca fabae, Psylla mali, Psylla piri, Trialeurodes vaporariorum, Aphis fabae, Aphis pomi, Aphis sambuci, Aphidula nasturtii, Cerosipha gossypii, Sappaphis mali, Sappaphis mala, Dysphis radicola, Brachycaudus cardui, Brevicoryne brassicae, Phorodon humuli, Rhopalomyzus ascalonicus, Myzodes persicae, Myzus cerasi, Dysaulacorthum pseudosolani, Acyrthosiphon onobrychis, Macrosiphon rosae, and Megoura viciae;
• mites and ticks belonging to the Arachnida class, e.g., Tetranychus urticae, Tetranychus atlanticus, Tetranychus pacificus, Paratetranychus pilosus, Bryobia praetiosa, Ixodes ricinus; Ornithodorus moubata, Ablyomma americanum, Dermacentor silvarum, and Boophilus microplus.
• insecticidal active ingredients employed were 1-naphthyl-N-methylcarbamate (carbaryl),2,5-diethylphenyl-N-methylcarbamate (fenethcarb), 2-dimethylamino-5,6-dimethyl-4-pyrimidinyl-N,N-dimethylcarbamate (pirimicarb), O,O-dimethyl-S-1,2-bis-carbethoxyethyl-(1)]-phosphorodithioate (malathion), DL-2-allyl-3-methylcyclopenten-2-on-(1)-yl-(4)-DL-cis,trans-chrysanthemate (allethrin), and an active ingredient mixture consisting of pyrethrin I, pyrethrin II, cinerin I and cinerin II from Chrysanthemum cinerae folium flowers (hereinafter designated "pyrethrins").
• pyrethrins an active ingredient mixture consisting of pyrethr
• the application rates are in logarithmic progression and permit a dose-effect curve to be drawn; the LD 50 is determined graphically and serves as a basis for assessment.
• insecticides used are carbaryl, fenethcarb, pirimicarb, malathion and allethrin; the ratio of insecticide to synergist is 1:5 parts by weight.
• the kill rate is determined after 4 hours and the LD 50 is determined graphically.
• the kill rate is determined, a dose-mortality curve is drawn from the different concentrations, and the LD 50 is worked out.
• Petri dishes 10 cm in diameter are lined with acetonic solutions of the active ingredients. After the solvent has evaporated, 50 granary weevils are placed in each dish.
• the kill rate is determined after 24 hours, by counting how many weevils are, after this period has elapsed, capable of leaving an untreated cardboard dish (40 mm in diameter, 10 mm high) within 60 minutes.
• aqueous active ingredient formulations active ingredient concentration in % is poured over 20 adult houseflies (Musca domestica) on a filter in a nutsch (15 cm in diameter). A gauze lid prevents the animals from surfacing during treatment. After 5 seconds the formulation is filtered off and the flies are transferred to clean Petri dishes (10 cm in diameter) on the bottom of which a round filter paper has been placed.
• the animals in supine position are counted after 4 and 24 hours.

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
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• 1978
  • 1978-07-28 DE DE19782833194 patent/DE2833194A1/de active Pending
• 1979
  • 1979-07-20 EP EP79102560A patent/EP0008651B1/de not_active Expired
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• 1980
  • 1980-03-28 US US06/135,914 patent/US4315017A/en not_active Expired - Lifetime

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